The reforming of methane with carbon dioxide has been investigated at 773 K on Rh/Al2O3 promoted with TiO2 and V2O5. In addition, the dissociation of carbon dioxide and methane has also been examined. TPR and XPS results revealed that during the pre-treatment of the catalysts not only Rh reduced but also TiO2 slightly and V2O5 significantly to V4+ below 600 K. The dissociation of carbon dioxide occurred most easily on vanadia promoted catalyst. Vanadia and titania promoted Rh/Al2O3 was found to be more active in the CO2 + CH4 reaction than the Rh/Al2O3. The increase of the conversion observed on V2O5 and TiO2 promoted Rh/Al2O3 catalysts could be attributed to the oxygen vacancies which formed on the additives during the pretreatment and the reaction. (C) 2011 Elsevier B. V. All rights reserved.